NZ550666A

NZ550666A - Method for removing cryptosporidium oocysts from water using chitosan

Info

Publication number: NZ550666A
Application number: NZ550666A
Authority: NZ
Inventors: Everett J Nichols; Jeffrey F Williams
Original assignee: Halosource Inc
Priority date: 2004-04-30
Filing date: 2005-04-28
Publication date: 2009-09-25
Also published as: EP1758826A4; EP1758826A2; WO2005108306A2; WO2005108306A3; US20050242043A1; AU2005240579A1; AU2005240579B2; BRPI0510194A; US7157009B2; CA2563211A1

Abstract

Disclosed is a method for removing Cryptosporidium oocysts or Giardia cysts from recreational water containing a halogenating agent, comprising exposing the Cryptosporidium oocysts or Giardia cysts to the halogenating agent for a period of time effective to oxidize at least a portion of the Cryptosporidium oocysts or Giardia cysts, adding chitosan to the water, allowing the Cryptosporidium oocysts or Giardia cysts and the chitosan to form stabilized flocs in the water, and filtering the flocs to remove the Cryptosporidium oocysts or Giardia cysts from the water.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number 550666 550666 WO 2005/108306 PCT/US2005/014928 METHOD FOR REMOVING CRYPTOSPORIDIUM OOCYSTS FROM WATER FIELD OF THE INVENTION Pathogens, such as Cryptosporidium oocysts and Giardia cysts, are removed from 5 water containing a halogenating agent by the addition of chitosan. The resulting floes of Ciyptosporidium oocysts or Giardia cysts and chitosan are then filtered to remove the Cryptosporidium oocysts or Giardia cysts from the water. BACKGROUND OF THE INVENTION Cryptosporidium is a water-borne parasitic protozoan responsible for the 10 water-borne disease Cryptosporidiosis. Outbreaks of Cryptosporidiosis have been attributed to ingestion of drinking water, recreational water or food containing viable oocysts of Cryptosporidium. Cryposporidium oocysts are typically introduced into the water through contamination of the water with fecal matter from cattle or humans containing oocysts. The oocysts have a hard outer cell wall that renders the oocysts 15 resistant to the effects of chlorine present at concentrations typical of drinking water and recreational water. The oocyts are approximately 4-6 microns in size, which makes them difficult to remove by filtration. Since filtration and chlorination are universally practiced as a means for clarifying and sanitizing drinking water in municipal water treatment facilities and for maintaining the clarity of recreational water such as in 20 swimming pools, water parks, hot tubs and spas, the chlorine resistance and size of the oocysts make it difficult to ensure that water is free of this disease-causing microorganism. A variety of filters and filter medias are used to clarify water in swimming pools, water parks, hot tubs and spas. Sand filters are common for swimming pool use and 25 municipal water treatment. Diatomaceous earth filters are also available for use in swimming pools and water parks. Cartridge filters available to both pools and spas utilize a synthetic fabric enclosed in a plastic cartridge. Different filter media exhibit different capabilities for removing particles that vary in size. Sand filters are capable of filtering out particles in the size range of 20-25 microns, while cartridge filters are 30 typically capable of removing particles in the size range of 5-10 microns. Diatomaceous earth filters exhibit the capability of removing particles in the size range of 1-3 microns, but have to be replaced frequently. -1- 550666 WO 2005/108306 PCT/l S2005/014928 Coagulation and flocculation followed by filtration is commonly utilized in the treatment of drinking and recreational water to remove suspended microscopic particles. Non-filterable suspended microscopic particles tend to possess an electrostatic charge that prevents the particles from aggregating into larger filterable aggregates due to 5 charge-charge repulsion. This can be often overcome through the use of coagulants and flocculants. Coagulants are chemicals, that when dissolved in water, form ions of charge opposite to that of the suspended particles. The charge interaction of the coagulant with the particles results in the reduction of the particle's charge or so called zeta potential. Reduction of the particle's zeta potential reduces particles' charge-charge repulsion and 10 allows the particles to come sufficiently close together to form aggregates large enough to be filtered out. The most commonly used coagulants are metal salts such as aluminum sulfate and ferric chloride and their use is highly dependent on both pH and dosage. Flocculants are typically water soluble or water dispersible high molecular weight polyelectrolyte long chain polymers composed of repeating monomelic units that can be 15 categorized into inorganic or organic compounds. The inorganic polyelectrolytes are polymerized metal salts and may include polyaluminum hydroxychloride, polyaluminum silicate sulfate and polyaluminum sulfate. Organic polyelectrolyte flocculants are derived synthetically or obtained from natural sources. The organic polyelectrolytes can exist as charged or uncharged polymers depending on their composition. Flocculants when added 20 to water containing aggregates of microscopic particles or non-aggregated particles exhibit the ability to bind and gather the particles or particle aggregates into even larger aggregates that can be easily filtered. The success of this aggregation is dependent on a variety of properties unique to the particles or particle aggregates and the properties of the particular flocculant being used. The stability of the flocculated particles or aggregated 25 particles can be important to successful removal by filtration. Unstable flocculated particles or particle aggregates may come apart during filtration and pass through the filter while only the more stable aggregates are retained. Aggregate stability can be influenced by the flow rate and pressure across the filter and the turbulence of the water. Previous attempts at removing Cryptosporidium oocysts via filtration from large 30 bodies of water moving at high flow rates have not been successful. Since Cryptosporidium oocysts are negatively charged, coagulants and flocculants such as ferric sulfate, ferric chloride, aluminum sulfate or polyaluminum chloride have been tried unsuccessfully as a means to remove the oocysts from water through the process of -2- 550666 WO 2005/108306 PCT/IS2005/014928 aggregation, settling and filtration. Although floes of oocysts are formed using these particular coagulants, the Cryptosporidium oocyst floes are unstable and subject to hydrodynamic shear forces that make them susceptible to breaking up and coming apart resulting in their not being retained on filters. The use of anionic or cationic polymeric 5 polyelectrolyte flocculants has been suggested as a means to stabilize Cryptosporidium oocyst-containing floes against shear. One such study involving dissolved air flotation (DAF) was performed using ferric sulfate as the primary coagulant and LT22, a cationic acrylamide co-polymer. No improvement in oocyst removal over that expected with ferric sulfate coagulant alone was observed. Sand filtration for removing 10 Cryptosporidium oocysts from water has been evaluated with some success. Rapid sand filtration has been reported to remove 3 logs of Cryptosporidium oocysts. Slow sand filtration that utilizes a finer grain of sand and a slower flow rate was reported in a pilot scale study to be fairly good in removing Cryptosporidium oocysts without having to use flocculants or coagulants. The previous coagulants and flocculants cannot be used in 15 conjunction with slow sand filtration because they tend to clog the pores and severely restrict the flow rate. Currently there is no methodology that is effective in stabilizing floes of Cryptosporidium oocysts for their significant removal from water through aggregation followed by filtration. Accordingly, there is a need to find a flocculant or coagulant or a 20 combination of the two for obtaining significant removal of oocysts that can take advantage of existing filtration technology such as sand, diatomaceous earth or synthetic cartridge filters to provide safe water for recreation and drinking. SUMMARY OF THE INVENTION The present invention relates to a method of removing Cryptosporidium oocysts 25 or Giardia cysts from water containing a halogenating agent. The method includes adding chitosan, chitosan salt, or a solution thereof to water containing Cryptosporidium oocysts or Giardia cysts and a halogenating agent. Before adding the chitosan to the water, the Cryptosporidium oocysts or Giardia cysts have been exposed to a halogenating agent for a period of time that is effective to oxidize at least a portion of the 30 Cryptosporidium oocysts or Giardia cysts. Adding chitosan to the water containing the Cryptosporidium oocysts or Giardia cysts and a halogenating agent will result in floes that are aggregates of Cryptosporidium oocysts or Giardia cysts and chitosan. Floes of Cryptosporidium oocysts or Giardia cysts with chitosan are stabilized so that the -3- 550666 WO 2005/108306 PCT/i;S2005/014928 Cryptosporidium oocysts or Giardia cysts can then be removed from the water by filtering the water in conventional filters. In other embodiments, a polyelectrolyte flocculant, other than the chitosan, and a coagulant can be added to the water before, after, or during the addition of the chitosan to 5 the water. The method according to the invention is particularly useful in water that is presently being treated with a halogenating agent, so that the addition of chitosan is supplemental and subsequent to treatment with a halogenating agent. However, the conventional treatments utilizing halogenating agents alone are ineffective in rendering 10 Cryptosporidium oocysts or Giardia cysts inactive. Treating water in a manner according to the invention will result in the flocculation of these pathogens into stabilized floes that can then be removed with the use of conventional filters. Pathogen contaminated water can come from swimming pools, water parks, hot tubs, spas, and any potable or nonpotable water sources. 15 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The term "chitosan" as used herein refers to a copolymer having greater than 65% by weight of 2-deoxy-2-aminoglucose monomeric units with the remainder of the monomelic units being 2-deoxy-2-acetamidoglucose units. Chitosan is derived from chitin by hydrolysis of some 2-deoxy-2-acetamidoglucose units to 20 2-deoxy-2-aminoglucose units. Due to the presence of free amino groups, chitosan is soluble in aqueous acidic solutions and is present in such media as a polycation with some of the protonated amino groups bearing a positive charge. One embodiment of a chitosan solution comprising chitosan and glacial acetic acid for use in the method according to the invention is known under the designation SEA-KLEAR, and is available 25 from Vanson HaloSource, Inc. of Redmond Washington. The term "halogenating agent" as used herein refers to compounds having a halogen atom bound to a strongly electronegative atom such as oxygen, nitrogen, or another halogen, and capable of donating a positively charged halogen atom. Representative halogenating agents include sodium hypochlorite, calcium hypochlorite, 30 chlorine, hypochlorous acid, bromine, hypobromous acid, aqueous chlorine solutions, aqueous bromine solutions, N-chlorosuccinimide, sodium hypobromite, pyridinium bromide perbromide, N-bromosuccinimide, chloramine-T, chlorhexadine, biguanides, dichlorodimethylhydantoin, bromochlorodimethylhydantoin, dibromodimethylhydantoin, -4- 550666 WO 2005/108306 PCT/l.'S2005.'014928 dichloroisocyanurate, trichloroisocyanurate, and combinations thereof. Other suitable halogenating agents will be readily apparent to those skilled in the art. Cryptosporidium oocysts (Cryptosporidium parvum) and Giardia cysts (Giardia duodenalis) are generally not inactivated with the levels of chlorine that are typical in 5 swimming pool, hot tub, spa, water park, potable and nonpotable water applications. Accordingly, an alternate method is removal of these pathogens that avoids resorting to such high levels of chlorine that would render the water unusable. However, even if the levels of chlorine are not sufficient to inactivate the pathogens, the levels of chlorine are sufficient to oxidize Cryptosporidium oocysts and Giardia cysts that can then be removed 10 with chitosan through flocculation and filtration. Cryptosporidium oocysts and Giardia cysts are known to have negative charges on their surfaces. However, the typical flocculants mentioned in the background section above have not proven successful for the flocculation and removal of Cryptosporidium oocysts. According to the present invention, chitosan is used to bond with Cryptosporidium oocysts or Giardia cysts to 15 produce stabilized floes of Cryptosporidium oocysts or Giardia cysts with chitosan. Chitosan has positively charged sites that bond to the negatively charged Cryptosporidium oocysts or Giardia cysts in a manner that produces a stabilized floe that allows for the removal of Cryptosporidium oocysts and Giardia cysts through filtration. The method according to the invention for removing Cryptosporidium oocysts or 20 Giardia cysts from water that already contains a halogenating agent comprises adding a dose of chitosan to the water already containing the halogenating agent. The amount of halogenating agent in water is preferably in the range of about 1 ppm to about 50 ppm by weight in water. More preferably about 2 ppm or about 3 ppm to about 20 ppm by weight in water. Preferably, the chitosan is dissolved in an acidic solvent to increase the 25 positively charged sites that can bond to Cryptosporidium oocysts or Giardia cysts. The situation of a halogenating agent already being present in water occurs in the context of swimming pools, spas, water parks, hot tubs, and any potable or nonpotable water source. Typically halogenating agents will be present in water that is treated on a routine basis for a purpose besides removing Cryptosporidium oocysts or Giardia cysts. One embodiment 30 of the present invention is the subsequent addition of chitosan to water containing a halogenating agent after the halogenating agent has had time to oxidize the Cryptosporidium oocysts or Giardia cysts. While the exact mechanism through which chitosan and the halogenating agent interact with a Cryptosporidium oocyst or Giardia -5- 550666 WO 2005/108306 PC 1/1 S2005/014*>28 cyst is not fully understood, one embodiment of the invention provides that sites on the Cryptosporidium oocysts or Giardia cysts be oxidized by the halogenating agent before addition of the chitosan. Oxidation is increased the longer that the Cryptosporidium oocysts or Giardia cysts are exposed to the halogenating agent. While the optimum 5 period of time that the halogenating agent should be given to oxidize sites on the Cryptosporidium oocysts or Giardia cysts is difficult to predict for any given situation, any water that has had a halogenating agent added to it before the addition of chitosan will realize some benefit of Cryptosporidium oocysts and Giardia cysts removal. As an approximation, the period of time to allow for oxidation between the Cryptosporidium 10 oocysts and the halogenating agent is from several days to several hours. However, some oxidation will occur even after a short period, such as an hour or less. Even at these shorter times, chitosan will produce floes of Cryptosporidium oocysts or Giardia cysts that can then be removed through filtration. When chitosan, a chitosan salt or an aqueous solution of a chitosan salt is in the presence of Cryptosporidium oocysts or Giardia cysts 15 that have been oxidized by a halogenating agent, the result will be stabilized aggregates or floes of the Cryptosporidium oocysts or Giardia cysts with the chitosan that can then be run through filters within a matter of minutes using the existing filters already installed in the water treatment system. Such filters can include sand filters, cartridge filters and diatomaceous earth filters. The floes of Cryptosporidium oocysts or Giardia cysts with 20 chitosan are stable under conditions of high water flow rates or velocities that may be encountered in swimming pool, hot tub, water park, spa and potable and nonpotable water filters. "Stable" or "stabilized" floe refers to the ability of a floe to substantially remain intact to allow a majority of the floe's removal through filtration under turbulent conditions or high velocities that are encountered in swimming pool, spa, hot tub, water 25 park, potable and nonpotable water filtration systems. Suitable levels of chitosan to cause flocculation of Cryptosporidium oocysts or Giardia cysts in water are about 5 ppb to about 100 ppm by weight. The pH of the water is believed to have an impact on the effectiveness with which any given halogenating agent will oxidize the Cryptosporidium oocysts or Giardia cysts. 30 For example, sodium hypochlorite exists in water as the anionic chlorite ion and the more oxidative hypochlorous acid. The relative amounts of each species depends on the pH of the water. In systems where pH can be adjusted without harmful effects, it may be -6- 550666 WO 2005/108306 P(T/i;S2005/014928 beneficial to lower the pH in the case of sodium hypochlorite to produce the more oxidative hypochlorous acid. In one embodiment of the present invention, a negatively or positively charged polyelectrolyte flocculant can be added to the water, before, after or during the addition 5 of the chitosan. Representative polyelectrolyte flocculants, in addition to chitosan, include alginate, hexametaphosphate, carboxymethylcellulose, pectin, polyaluminum hydroxychloride, polyaluminum silicate sulfate, polyaluminum sulfate and polyacrylamide. A negatively charged anionic polyelectrolyte flocculant, for example, will combine with the cationic polyelectrolyte chitosan (bound to the Cryptosporidium 10 oocysts or Giardia cysts) to form a polyelectrolyte complex of larger floes containing aggregates of Cryptosporidium oocysts or Giardia cysts that are removed from the water by entrapment on a filter. This is particularly effective for filters with larger nominal pore sizes. Suitable levels of polyelectrolyte flocculants in water, not including chitosan, are about 5 ppb to about 100 ppm by weight. 15 In another embodiment of the present invention, a coagulant can be added to the water, before, after or during addition of the chitosan, including with or without the polyelectrolyte flocculant. Representative coagulants include inorganic aluminum or ferric salts, such as ferric or aluminum sulfate or chloride. Suitable levels of coagulant in the water are about 50 ppb to about 100 ppm by weight. 20 EXAMPLE 1 DEMONSTRATION OF INCREASED FLOC SIZE USING BOTH CHITOSAN AND ALGINATE IN WATER CONTAINING A HALOGENATING AGENT One liter of deionized water was mixed with about 0.03-0.08 grams of dichlor (a chlorine source). A small drop (~0.02 grams) of NIVEA lotion or 2 grams of a 25 solution consisting of 0.1 gram NIVEA lotion in 9.9 grams of distilled water was then added to the 1 liter of water containing dichlor. A cloudy solution develops upon mixing. Control water contained all ingredients except dichlor (chlorine source). SEA-KLEAR for spas (0.5% chitosan and 0.5 % acetic acid in water wt./wt.) was then added dropwise (10 drops ~0.4 grams) to the test solution and allowed to mix for about 2-5 minutes. 30 Mixing was stopped and small floes formed within ~ 5 minutes in the dichlor-containing water but not the control water that did not contain dichlor. Mixing was started again and 1 drop (0.04 gram) of a 1 % (wt./wt.) sodium alginate in water solution was added. Solution was mixed for about 2-5 minutes, stopped and floe size was measured. Floe size -7- </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 550666 WO 2005/108306 PCT/IS2005/014928 increased in comparison to the same solution without sodium alginate. Control solutions without chlorine did not form floes. Dichlor Presence Chitosan Alginate Floe Size (chlorine source) (Primary Flocculant) (Secondary Flocculant) (nominal) Yes Yes Yes 2,000-4,000 microns Yes Yes No 500 microns No Yes Yes none No Yes No none 5 Results demonstrate that addition of a secondary anionic polymer flocculant to a solution containing chitosan, chlorine and NIVEA lotion can increase the size of flocculated material, which is not observed in non-chlorine containing water. While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without 10 departing from the spirit and scope of the invention. -8- 550666 WHAT WE CLAIM IS:

1. A method for removing Cryptosporidium oocysts or Giardia cysts from recreational water containing a halogenating agent, comprising: adding chitosan to the water comprising Cryptosporidium oocysts or Giardia cysts and a halogenating agent, wherein the Cryptosporidium oocysts or Giardia cysts have been exposed to the halogenating agent for a period of time effective to oxidize at least a portion of the Cryptosporidium oocysts or Giardia cysts, before add ing the chitosan to the water; allowing the Cryptosporidium oocysts or Giardia cysts and the chitosan to form stabilized floes in the water; and filtering the floes of the Cryptosporidium oocysts or Giardia cysts and chitosan to remove the Cryptosporidium oocysts or Giardia cysts from the water.

2. The method of claim 1, wherein the chitosan is in solution.

3. The method of claim 2, wherein the solution comprises acetic acid.

4. The method of claim 1, further comprising adding an anionic or cationic polyelectrolyte flocculant to the water before, during or after adding the chitosan.

5. The method of claim 4, wherein the polyelectrolyte flocculant comprises at least one of alginate, hexametaphosphate, carboxymethylcellulosc, pectin, polyaluminum hydroxychloride, polyaluminum silicate sulfate, polyaluminum sulfate or polyacrylamide.

6. The method of claim 4, wherein said polyelectrolyte flocculant is 5 ppb to 100 ppm by weight in water.

7. The method of claim 1, wherein the water is in a swimming pool, spa, water park, hot tub, or bath.

8. The method of claim 1, comprising filtering the floes in at least one of a -9- 1 AUb 2MB 550666 sand, cartridge or diatomaceous earth filter.

9. The method of claim 1, further comprising adding an inorganic aluminum coagulant.

10. The method of claim 9, wherein said inorganic aluminum coagulant is aluminum sulfate or polyaluminum chloride.

11. The method of claim 9, wherein the inorganic aluminum coagulant is 50 ppb to 100 ppm by weight in water.

12. The method of claim 1, further comprising adding a ferric salt coagulant.

13. The method of claim 12, wherein said ferric salt coagulant is ferric sulfate or ferric chloride.

14. The method of claim 12, wherein said ferric salt coagulant is 50 ppb to 100 ppm by weight in water.

15. The method of claim 1, wherein said chitosan is 5 ppb to 100 ppm by weight in water. .

16. The method of claim 1, wherein the halogenating agent comprises at least one of sodium hypochlorite, calcium hypochlorite, chlorine, hypochlorous acid, bromine, hypobromous acid, N-chlorosuccinimide, sodium hypobromite, pyridinium bromide perbromide, N-bromosuccinimide, chloramine-T, chlorhexadine, biguanides, dichlorodimethylhydantoin, bromochlorodimethylhydantoin, dibromodimethylhydantoin, dichloroisocyanurate, or trichloroisocyanurate.

17. The method of claim 1, wherein said halogenating agent is 1 ppm to 50 ppm by weight in water.

18. The method of claim 1, wherein said halogenating agent is 2 ppm to 20 ppm by weight in water. - 10- 550666

19. The method of claim 1, comprising adding a halogenating agent to the water before adding chitosan.

20. A method according to claim 1 substantially as herein described with reference to any example thereof. </div>